Organic Letters
Letter
Geier, J.; Breit, B. Angew. Chem., Int. Ed. 2009, 48, 8022. (f) Boogaerts,
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2
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̈
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H. M. J. Organomet. Chem. 2000, 593−594, 211. (j) Konya, D.;
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(
k) Knifton, J. F. J. Mol. Catal. 1987, 43, 65. (l) Fleischer, I.; Dyballa,
K. M.; Jennerjahn, R.; Jackstell, R.; Franke, R.; Spannenberg, A.; Beller,
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Jackstell, R.; Profir, I.; Franke, R.; Beller, M. J. Am. Chem. Soc. 2013,
1
(
35, 14306.
5) (a) Takahashi, K.; Yamashita, M.; Ichihara, T.; Nakano, K.;
Nozaki, K. Angew. Chem., Int. Ed. 2010, 49, 4488. (b) Takahashi, K.;
Yamashita, M.; Nozaki, K. J. Am. Chem. Soc. 2012, 134, 18746.
(
2
c) Yuki, Y.; Takahashi, K.; Tanaka, Y.; No zaki, K. J. Am. Chem. Soc.
013, 135, 17393.
6) (a) Blum, Y.; Shvo, Y. J. Organomet. Chem. 1985, 282, C7.
b) Blum, Y.; Shvo, Y.; Chodosh, D. F. Inorg. Chim. Acta 1985, 97,
(
(
L25. (c) Shvo, Y.; Czarkie, D.; Rahamim, Y.; Chodosh, D. F. J. Am.
Chem. Soc. 1986, 108, 7400. (d) Casey, C. P.; Johnson, J. B.; Singer, S.
W.; Cui, Q. J. Am. Chem. Soc. 2005, 127, 3100. (e) Casey, C. P.;
Singer, S.; Powell, D. R.; Hayashi, R. K.; Kavana, M. J. Am. Chem. Soc.
2
001, 123, 1090. (f) Casey, C. P.; Beetner, S. E.; Jhonson, J. B. J. Am.
Chem. Soc. 2008, 130, 2285. (g) Comas-Vives, A.; Ujaque, G.; Lledos
A. Organometallics 2008, 27, 4854.
́
,
(
7) For example, the TOF at 60 °C by 1 under H /CO = 1:1 was
2
3
1
h from our results and in the absence of
estimated to be 4.9 × 10
carbon monoxide reported as 3.2 × 10 h by Casey et al. (ref 6e),
which corresponds to ΔG = +28.5 kcal/mol and +21.2 kcal/mol,
respectively.
2
1
⧧
(
8) Choi, J. H.; Choi, Y. K.; Kim, Y. H.; Park, E. S.; Kim, E. J.; Kim,
M.-J.; Park, J. J. Org. Chem. 2004, 69, 1972.
9) Ito, M.; Hirakawa, M.; Osaku, A.; Ikariya, T. Organometallics
003, 22, 4190.
10) Jia, W.; Chen, X.; Guo, R.; Sui-Seng, C.; Amoroso, D.; Lough, A.
J.; Abdur-Rashid, K. Dalton Trans. 2009, 8301.
11) (a) Menashe, N.; Shvo, Y. Organometallics 1991, 10, 3885.
b) Do, Y.; Ko, S.-B.; Hwang, I.-C.; Lee, K.-E.; Lee, S.-W.; Park, J.
Organometallics 2008, 28, 4624.
12) The relative electron densities of Ru center of 7, 8, 9, and 10
were estimated from IR bands for ligand CO stretch. The values
(
2
(
(
(
(
1
were (complex: νCO (cm )) = (7: 2066, 2011, 1989), (8: 2100,
029, 2002), (9: 2070, 2006), (10: 2081, 2026, 2005), which
represented the order of electron densities as 7 ≈ 9 > 10 > 8.
13) Examples of trap of coordinatively unsaturated 16e species by
2
(
carbon monoxide are reported for Cp*Ru(PN) complex in: Wylie, W.
N. O.; Lough, A. J.; Morris, R. H. Organometallics 2011, 31, 2137. For
the results for Ru(PN) complex, see: Wylie, W. N. O.; Lough, A. J.
2
Inorg. Chim. Acta 1998, 268, 69.
(
14) For previous experimental and/or computational studies, see ref
d,g for Shvo’s complex and ref 9 for the Cp*Ru(PN) complex. The
RuP N systemis discussed in: Hedberg, C.; Kallstrom, K.; Arvidsson,
6
2
2
̈
̈
P. I.; Brandt, P.; Andersson, P. G. J. Am. Chem. Soc. 2005, 127, 15083.
A trace amount of water may have provided a proton at the beginning
of the reaction. Similar acceleration by proton was reported in ref 6d.
(
15) Reaction pathways free of methanol were also calculated to
prove the higher energy barriers for the process with 10−12. Full
computational results for 2 and 9−12 are summarized in the
Supporting Information.
D
dx.doi.org/10.1021/ol502681y | Org. Lett. XXXX, XXX, XXX−XXX